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KR101157742B1 - 도전성 접합 재료, 그것을 이용한 접합 방법, 및 그것에 의하여 접합된 반도체 장치 - Google Patents

도전성 접합 재료, 그것을 이용한 접합 방법, 및 그것에 의하여 접합된 반도체 장치 Download PDF

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Publication number
KR101157742B1
KR101157742B1 KR20100038827A KR20100038827A KR101157742B1 KR 101157742 B1 KR101157742 B1 KR 101157742B1 KR 20100038827 A KR20100038827 A KR 20100038827A KR 20100038827 A KR20100038827 A KR 20100038827A KR 101157742 B1 KR101157742 B1 KR 101157742B1
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South Korea
Prior art keywords
silver
particles
bonding material
less
metal
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KR20100038827A
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English (en)
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KR20100118524A (ko
Inventor
유우스께 야스다
도시아끼 모리따
에이이찌 이데
데이이찌 이나다
Original Assignee
히다치 가세고교 가부시끼가이샤
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Publication of KR20100118524A publication Critical patent/KR20100118524A/ko
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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Abstract

본 발명은 평균 입경이 100 nm 이하인 금속 입자를 이용한 접합용 재료와 비교하여, 접합 계면에서 금속 결합에 의한 접합을 보다 저온에서 또한 무가압에서 접합 강도의 향상을 실현 가능한 접합용 재료, 접합 방법을 제공한다.
본 발명은, (A) 은 입자, (B) 산화은, (C) 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제를 필수 성분으로 하는 전체 도전성 접합 재료 중에서, (A) 은분과 (B) 산화은분과 (C) 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제의 합계가 99.0 내지 100 중량％로 되어 있다. 즉, 결합제로서 수지가 함유되어 있지 않은 것을 특징으로 한다.

Description

도전성 접합 재료, 그것을 이용한 접합 방법, 및 그것에 의하여 접합된 반도체 장치{CONDUCTIVE BONDING MATERIAL, METHOD FOR BONDING USING THE SAME, AND SEMICONDUCTOR DEVICE BONDED BY THE SAME}
본 발명은 도전성 접합 재료, 그것을 이용한 접합 방법, 및 그것에 의하여 접합된 반도체 장치에 관한 것으로서, 예를 들면, 반도체 모듈에서 이용되는 접합 재료 및 접합 방법에 관한 것이다.
인버터 등에 이용되는 파워 반도체 장치의 하나인 비절연형 반도체 장치에 있어서, 반도체 소자를 고정하는 부재는 반도체 장치의 전극의 하나이기도 하다. 예를 들면, 파워 트랜지스터를 고정 부재 상에 Sn-Pb계 납땜재를 이용하여 탑재한 반도체 장치에서는, 고정 부재(베이스재)는 파워 트랜지스터의 콜렉터 전극이 된다. 이 콜렉터 전극에는 반도체 장치 가동 시에는 수 암페어 이상의 전류가 흘러 트랜지스터칩은 발열한다. 이 발열에 기인하는 특성의 불안정화나 수명의 저하를 피하기 위해서는, 납땜부의 방열성, 장기간 신뢰성(내열성)이 확보되어야만 한다. 이 때문에, 이 납땜부의 내열성 및 방열성의 확보에는 고방열성의 재료가 필요하게 되어 온다.
절연형 반도체 장치에 있어서도, 반도체 소자를 안전하고 또한 안정적으로 동작시키기 위해서는, 반도체 장치의 동작 시에 발생하는 열을 반도체 장치의 밖으로 효율 좋게 방산시키고, 또한 납땜부의 접속 신뢰성을 확보할 필요가 있다. 예를 들면, 자동차의 엔진룸은 고온인 상태가 되는 경우가 많아, 이러한 환경 하에서도 접합 부분의 신뢰성에 문제가 없어야 한다.
접합 부분의 내열성을 높이기 위해서는 고융점의 접합 재료를 사용하면 좋지만, 이 경우 접합 온도도 높아져 버린다. 접합 온도가 고온이 되면 고정하는 부재가 열에 의해서 손상되어 버리거나, 접합 후 냉각 시에 있어서의 기판과 부재와의 응력차에 의해서 반도체 장치 전체에 변형이 생겨 버리는 경우도 있다. 즉, 접합 재료의 내열성은 높이고자 하지만, 접합 온도는 낮추고자 하는 요구가 있다.
예를 들면, 특허문헌 1에 기재되어 있는 바와 같이, 높은 방열성과 신뢰성을 갖는 접속 재료로서, 입자상 은 화합물을 포함하는 도전성 조성물을 이용한 도전성 접착제가 알려져 있다.
또한, 특허문헌 2에 있어서는 1 내지 100 ㎛ 크기의 입자를 접합층 중에서 소결시키는 수법이 보고되어 있다.
또한, 금속 입자의 입경이 100 nm 이하의 크기까지 작아져 구성 원자수가 적어지면, 입자의 부피에 대한 표면적비는 급격히 증대하여, 소결 온도가 벌크 상태에 비하여 대폭 저하된다는(소결성이 높아지거나, 또는 표면 에너지가 커짐) 것이 알려져 있다. 예를 들면, 특허문헌 3에는, 이 저온 소성 기능을 이용하여, 유기물로 표면이 피복된 평균 입경 100 nm 이하의 금속 입자를 접합 재료로서 이용하고, 가열에 의해 유기물을 분해시켜 금속 입자끼리를 소결시킴으로써 접합을 행하는 것이 기재되어 있다. 이 접합 방법에서는, 접합 후의 금속 입자는 벌크 금속으로 변화함과 동시에 접합 계면에서는 금속 결합에 의해 접합되어 있기 때문에 매우 높은 내열성과 신뢰성 및 고방열성을 갖는다.
일본 특허 공개 제2003-309352 일본 특허 공개 제2005-129303 일본 특허 공개 제2004-107728 일본 특허 공개 제2008-161907 일본 특허 공개 제2008-178911
그러나, 특허문헌 1 및 2에 기재된 접합 재료(도전성 접착제)는 계면에서의 접합 기구가 수지로 이루어지는 결합제를 이용한 방법이기 때문에, 계면에서 금속 결합을 달성한 경우와 비교하면, 방열성 및 접합 신뢰성이라는 점에서는 떨어진다.
또한, 특허문헌 3에 기재된 접합 재료에서는, 평균 입경이 100 nm 이하인 금속 입자를 이용하고 있지만, 상술한 바와 같이, 접합 계면에서는 금속 결합에 의한 접합이 행하여지고 있기 때문에 높은 내열성과 신뢰성 및 고방열성을 갖는다. 그 반면, 평균 입경이 100 nm 이하로 매우 미세한 금속 입자는 응집을 일으키기 쉽고, 이러한 금속 입자는 안정화시키기 위해서 유기물의 보호막을 형성할 필요가 있다. 이 유기물의 보호막은 접합 시에는 제거할 필요가 있는데, 그 때에 입자 표면에서 대량의 유기물이 휘발하여 부피 수축을 일으키기 때문에, 접합 시에 가압할 필요가 있다. 접합 시에 가압하면 반도체칩에 대한 손상을 제공하게 될 우려가 있다. 또한, 통상 납땜의 공정에는 가압하는 공정은 없기 때문에, 이 수법을 적용하기 위해서는 접합 시에 가압하기 위한 공정(설비)가 필요해져서 범용성이 부족하다. 이와 같이, 평균 입경이 100 nm 이하인 금속 입자를 이용한 접합 방법에서는, 금속 입자의 제작, 제작 후의 불순물의 제거나 보관, 취급 등, 실용면에서의 과제가 남겨져 있다.
본 발명은 이러한 상황을 감안하여 이루어진 것으로서, 접합 후에는 내열성이 우수하고, 접합 시에는 수지를 함유한 도전성 접합 재료와 비교하여 접합 계면에서의 금속 결합을 보다 저온에서 실현 가능하고, 접합 공정에서 가압을 필수로 하지 않는 무가압에서의 접합이 가능한 도전성 접합 재료 및 그것을 이용한 접합 방법, 및 그것에 의하여 접합된 반도체 장치를 제공하는 것이다.
상기 과제를 해결하기 위해서 본 발명에서는 지금까지 주목되고 있지 않았던 입경이 0.1 내지 100 ㎛(마이크로 입자)인 은분(은 입자)와 산화은분(산화은 입자)를 이용함으로써 접합부의 금속 접합을 가능하게 하고 있다. 또한, 수지를 이용하지 않음(유기물의 함유량을 적게 함)으로써, 접합 과정에서의 무가압화를 가능하게 하여 접합 공정의 간략화를 달성한다.
또한, 땜납의 납프리 대응이 재촉되고 있지만, 고온 땜납에 대해서는 그 대체가 되는 재료가 나와 있지 않다. 실장에 있어서는 계층 땜납을 이용하는 것이 필요 불가결이기 때문에, 이 고온 땜납을 대신할 재료의 출현이 요망되고 있다. 따라서, 본 접합 기술은 이 고온 땜납을 대신할 재료로서도 기대되고 있다.
본 발명자들은 (A) 은분, (B) 산화은분, (C) 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제 필수 성분으로 하는 전체 도전성 접합 재료 중에서, (A) 은분과 (B) 산화은분과 (C) 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제의 합계가 99.0 내지 100 중량％인 것을 특징으로 하는 도전성 접합 재료를 이용함으로써, 200℃ 이하라는 저온에서 은 입자의 소결이 개시되고, 또한 무가압에서의 접합이 가능한 것을 발견하였다. 이 때, 혼합한 산화은 입자가 유기물을 포함하는 분산제와 150℃ 이하 저온에서 산화환원 반응을 일으켜 은으로 환원하고, 그 때에 융합을 일으키기 때문에, 200℃ 이하에서의 소결을 진행시켜, 은 입자 단체로 이용한 경우보다도 한층더 접합 강도의 향상을 가능하게 한다. 또한, 본 발명자들은 이 때에는 수지의 결합제를 이용하지 않고서 접합 재료에 이용한 은 입자와 산화은 입자로부터 환원한 은에 의해 상대 전극과의 접합이 가능한 것을 발견하였다.
즉, 본 발명에 의한 도전성 접합 재료는 은 입자와, 산화은 입자와, 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제를 필수 성분으로 하고, 은 입자와 산화은 입자와 분산제의 합계가 99.0 내지 100 중량％인 것을 특징으로 한다. 여기서는 은 입자와 산화은 입자의 입경이 0.1 ㎛ 이상 100 ㎛ 이하이다. 은 입자가 플레이크상의 형상을 하도록 할 수도 있다. 또한, 은 입자 및 산화은 입자의 적어도 한쪽이 분산제에 의해 피복되어 있다. 산화은 입자의 양은 분산제의 양 이하인 것이 바람직하다. 또한, 은 입자와 산화은 입자의 혼합율은, 은 입자를 100 질량부로 한 경우에 산화은 입자가 0.01 질량부 이상 100 질량부 이하이다.
다른 양태의 도전성 접합 재료는 은 입자와, 산화은 입자와, 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제와, 비점이 350℃ 이하인 유기 용제를 필수 성분으로 하며, 은 입자와 산화은 입자와 분산제와 유기 용제의 합계를 100 질량부로 한 경우에, 유기 용제의 양이 90 질량부 이하이고, 은 입자와 산화은 입자와 분산제와 유기 용제와의 합계가 99.0 내지 100 중량％이고, 페이스트상을 하고 있는 것을 특징으로 한다.
또한, 다른 양태의 도전성 접합 재료는 은 입자와, 산화은 입자와, 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제와, 은 이외의 금속 입자를 필수 성분으로 하고, 은 입자와 산화은 입자와 분산제와 은 이외의 금속 입자와의 합계가 99.0 내지 100 중량％인 것을 특징으로 한다.
또한, 다른 양태의 도전성 접합 재료는 은 입자와, 산화은 입자와, 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제와, 비점이 350℃ 이하인 유기 용제와, 은 이외의 금속 입자를 필수 성분으로 하며, 은 입자와 산화은 입자와 분산제와 유기 용제와 금속 입자의 합계를 100 질량부로 한 경우에, 유기 용제의 양이 90 질량부 이하이고, 은 입자와 산화은 입자와 분산제와 유기 용제와 은 이외의 금속 입자와의 합계가 99.0 내지 100 중량％이고, 페이스트상을 하고 있는 것을 특징으로 한다.
본 발명에 의한 반도체 장치는 상술한 어느 하나의 도전성 접합 재료를 이용하여 접합되고, 접합부가 금속 부분만으로 이루어지고, 그의 공극률이 0.1％보다 크고 90％보다 작은 것을 특징으로 한다.
본 발명에 의한 접합 방법은 반도체 소자의 전극과 금속 부재와의 사이에 상술한 어느 하나의 도전성 접합 재료를 배치하고, 수소 중, 질소 중 또는 아르곤 분위기 중에서 가열함으로써 도전성 접합 재료를 소결시켜 반도체 소자의 전극과 금속 부재를 금속 접합하는 것을 특징으로 한다.
한층더 본 발명의 특징은 이하 본 발명을 실시하기 위한 최선의 형태 및 첨부 도면에 의해서 분명해지는 것이다.
본 발명에 따르면, 평균 입경이 100 nm 이하인 금속 입자를 이용한 접합용 재료와 비교하여, 접합 계면에서의 금속 결합에 의한 접합을 보다 저온에서 실현 가능한 접합용 재료, 접합 방법을 제공할 수 있다. 또한, 수지와 같은 결합제를 이용하지 않기 때문에 무가압으로 접합 공정을 구축할 수 있어, 접합 후에서의 접합부의 고내열화, 고방열화가 가능해진다.
도 1은 은 플레이크와 산화은 입자를 이용하여 접합을 행했을 때의 개념도이다.
도 2는 은 플레이크에 산화은 입자를 가한 경우의 접합 강도 변화를 도시한 도면이다.
도 3은 은 플레이크에 가하는 산화은 입자의 비율의 영향을 도시한 도면이다.
도 4는 본 발명의 실시예의 하나인 비절연형 반도체 장치의 구조를 도시한 도면이다.
도 5는 본 발명 절연형 반도체 장치의 서브어셈블리부를 도시한 도면이다.
도 6은 반도체 소자와 기판 접합부의 확대 개략도이다.
도 7은 본 실시예 절연형 반도체 장치의 단면 모식도이다.
도 8은 본 실시예 미니 몰드형 비절연형 반도체 장치의 단면 모식도이다.
이하, 본 발명의 실시 형태에 대해서 구체적으로 설명하고, 계속해서 실시예 및 적용예에 대해서 설명한다.
<접합 재료의 조성>
본 발명은 (A) 은분과, (B) 산화은분과, (C) 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제를 필수 성분으로 하는 전체 도전성 접합 재료에 관한 것이다. 이러한 조성을 갖는 도전성 접합 재료에 있어서, (A) 은분과 (B) 산화은분과 (C) 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제의 합계가 99.0 내지 100 중량％로 되어 있다. 즉, 종래의 수지는 포함되지 않는 구성으로 되어 있다. 접합 시에 이 도전성 접합 재료를 가열하여, 은 입자와 산화은 입자를 소결시켜 금속적인 접합을 행한다. 은분에 산화은을 혼합시킴으로써, 접합 시에 분산제와 산화은이 150℃ 이하의 온도로 산화환원 반응을 일으켜, 은분의 소결을 촉진함으로써 저온에서의 접합 강도 향상이 가능해진다.
또한, 본 발명에 있어서의 접합 재료를 이용한 접합 기구는 수지를 이용하지 않는 금속 접합이기 때문에, 접합 후에 있어서의 접합부의 고내열화, 고방열화가 가능해진다. 이와 같이 저온에서 금속 접합이 가능하기 때문에, 예를 들면, 반도체 소자의 액티브 에리어 상에 설치한 전극과 이것을 탑재하는 배선 기판의 탑재부와의 접합에 적용 가능하다. 또한, 접합 후의 접합층은 종래의 땜납재와 비교하여 높은 내열성을 갖고 있기 때문에, 이차 실장 등의 열 공정에서 반도체 소자 탑재부의 용융 등의 문제도 없고, 반도체 장치의 소형화와 고신뢰화를 실현할 수 있다.
또한, 해당 접합 재료에 따르면, 평균 입경 100 nm 이하의 금속 나노 입자를 이용한 경우보다도 무가압에서의 대폭적인 접합 강도 향상이 가능해진다. 이에 따라, 종래 기술에서는 곤란하였던 무가압 하에서의 금속 접합이 가능해져, 접합 시의 가압 공정의 생략이 가능해져, 접합 공정의 대폭적인 간략화가 가능해진다. 또한, 접합 시에 가압하지 않기 때문에, 반도체칩 등에 대한 접합 시의 손상을 크게 경감할 수 있다.
<입자의 크기 및 형상>
여기서 이용하는 은 입자와 산화은 입자의 입경은 평균 입경이 0.1 ㎛ 이상 100 ㎛ 이하로 하고 있다. 금속 입자의 평균 입경 100 ㎛보다 커지면 도전성 접합 재료 중에서의 분산성이 나빠져서, 치밀한 접합층을 얻는 것이 곤란해지기 때문이다. 또한, 평균 입경을 0.1 ㎛ 이상으로 한 것은, 평균 입자가 0.1 ㎛ 이하인 금속 입자를 제작하기 위해서는 많은 유기물로 금속 입자의 주위를 피복할 필요가 있고(이 유기물은 평상 상태에서 입자끼리가 결합하여 버리는 것을 방지하기 위한 것임), 그와 같은 입자를 접합에 이용하면 그 유기물을 제거할 때에 부피 수축이 발생하기 때문에, 무가압에서의 접합이 곤란해지기 때문이다.
산화은 입자로서는 Ag2O나 AgO 등을 들 수 있고, 이들 중으로부터 1종 이상의 금속 또는 2종의 금속으로 이루어지는 접합 재료를 이용하는 것이 가능하다. 또한, 산화은 입자 이외에도 산화금, 산화구리를 포함하는 금속 산화물을 동시에 첨가하여 이용할 수도 있다.
이용하는 산화은과 은 입자의 형상은 플레이크상으로 이루어지는 것을 이용하는 것이 가능하다(후술된 실시예(도 1 등)에서는 은 입자만이 플레이크 형상으로 되어 있음). 플레이크상의 평균 입경은 100 ㎛ 이하가 바람직하고, 보다 바람직하게는 50 ㎛ 이하, 가장 바람직하게는 10 ㎛ 이하이다. 하한은 0.1 ㎛ 이상이 바람직하다. 평균 입경이 100 ㎛을 초과하면 스크린 인쇄를 하는 경우에는 스크린에 클로깅을 일으키거나, 상기 플레이크상 입자의 침강에 의한 페이스트의 저장 안정성이 저하될 가능성이 있다. 한편, 평균 입경이 0.1 ㎛ 미만이면 페이스트의 점도가 높게 되어 상기 플레이크상 입자를 충분 충전할 수 없게 될 가능성이 있다.
또한, 이 플레이크상 입자는 평균 두께가 5.0 ㎛ 이하인 것이 바람직하고, 보다 바람직하게는 1 ㎛ 이하이다. 하한은 특별히 한정되지 않지만, 0.1 ㎛ 이상이 바람직하다. 2.0 ㎛ 초과에서는 종횡비가 작아져 도전성이 저하될 가능성이 있다.
또한, 이 플레이크상 입자의 종횡비는 1.0보다 위가 바람직하고, 2 이상이 보다 바람직하다. 상한은 특히 정하는 것이 아니지만, 200 이하가 바람직하고, 보다 바람직하게는 150 이하이다.
또한, 입자 형상은 상술한 구상이나 플레이크상에 한하지 않고, 사면체나 팔면체, 로드상, 섬유상의 것을 이용하는 것이 가능하다. 플레이크 형상의 경우, 입자끼리가 면에서 접할 수가 있기 때문에, 접촉 면적은 커진다.
<은 입자와 산화은 입자의 혼합율>
은 입자와 산화은 입자의 혼합율은 은 입자 100 질량부에 대하여 산화은 입자를 0.01 질량부 이상 100 질량부 이하의 범위로 하는 것이 좋다. 0.01 질량부 이상으로 한 것은 이것보다 적으면 산화은으로부터의 환원은의 양도 적어져, 저온에서의 은 입자를 융합하는 효과가 나타나지 않게 되기 때문이다. 100 질량부 이하로 한 것은, 이것보다도 가하는 산화은 입자의 양이 많아지면 접합층에 있어서 산화은의 부피 수축이 차지하는 비율이 많아져, 결과로서 접합 강도가 저하하도록 되기 때문이다. 접합 강도를 고려하면, 보다 바람직하게는 40 중량％ 정도가 바람직하다(도 3 참조).
<분산제의 예>
탄소수 30 이하의 유기물을 포함하는 분산제(또한, 산화은의 환원제)로서는 알코올류, 카르복실산류, 아민류로부터 선택된 1종 이상의 혼합물을 사용할 수 있다. 이들은 혼합 입자의 용매에의 금속 입자의 주위를 유기물로 피복하여, 유기 용제에 대한 분산성을 향상시키는 작용이 있다. 여기서, 분산제(은 입자끼리가 부착하지 않도록 하기 위한 것)로서 예를 들면 스테아르산을 이용한 경우, 산화은과, 은 입자에 부착되어 있었던 스테아르산이 140 내지 150℃에서 환원 반응을 일으켜, 스테아르산이 은 입자로부터 제거된다. 이 때문에, 산화은의 혼합 비율이 스테아르산의 양에 비하여 너무 많으면 충분히 환원 반응을 일으킬 수 없어서 산화은이 접합재 내에 남게 된다. 이래서는 접합 강도가 높아지지 않는다. 따라서, 산화은과 분산제의 혼합비는 1대1을 한도로 하는 것이 바람직하다.
여기서, 탄소수 30 이하로 한 것은, 탄소수가 너무 많아지면, 분산제의 비점이 높게 되어 버려, 접합 시에 가열(예를 들면 200℃)하더라도 분산제가 접합 부분에 남게 되어, 접합 강도 및 신뢰성에 문제가 될 가능성이 있기 때문이다.
또한, 이용 가능한 알코올기를 포함하는 화합물로서는 알킬알코올을 들 수 있어, 예를 들면, 에탄올, 프로판올, 부틸알코올, 펜틸알코올, 헥실알코올, 헵틸알코올, 옥틸알코올, 노닐알코올, 데실알코올, 운데실알코올, 도데실알코올, 트리데실알코올, 테트라데실알코올, 펜타데실알코올, 헥사데실알코올, 헵타데실알코올, 옥타데실알코올, 노나데실알코올, 이코실알코올이 있다. 나아가서는 1급 알코올형에 한하지 않고, 2급 알코올형, 3급 알코올형, 및 알칸디올, 환상형의 구조를 갖는 알코올 화합물을 이용하는 것이 가능하다. 그것 이외에도, 에틸렌글리콜, 트리에틸렌글리콜, 또는 시트르산, 아스코르브산, 글루코오스 등 다수의 알코올기를 갖는 화합물을 이용할 수도 있다.
또한, 이용 가능한 카르복실산을 포함하는 화합물로서 알킬카르복실산이 있다. 구체예로서는, 부탄산, 펜탄산, 헥산산, 헵탄산, 옥탄산, 노난산, 데칸산, 운데칸산, 도데칸산, 트리데칸산, 테트라데칸산, 펜타데칸산, 헥사데칸산, 헵타데칸산, 옥타데칸산, 노나데칸산, 이코산산, 올레산을 들 수 있다. 또한, 상기 알코올기와 같이 1급 카르복실산형에 한하지 않고, 2급 카르복실산형, 3급 카르복실산형, 및 디카르복실산, 환상형의 구조를 갖는 카르복실 화합물을 이용하는 것이 가능하다.
또한, 이용 가능한 아미노기를 포함하는 화합물로서 알킬아민을 들 수 있다. 예를 들면, 부틸아민, 펜틸아민, 헥실아민, 헵틸아민, 옥틸아민, 노닐아민, 데실아민, 운데실아민, 도데실아민, 트리데실아민, 테트라데실아민, 펜타데실아민, 헥사데실아민, 헵타데실아민, 옥타데실아민, 노나데실아민, 이코데실아민이 있다. 아미노기를 갖는 화합물로서는 분지 구조를 갖고 있을 수도 있고, 그와 같은 예로서는, 2-에틸헥실아민, 1,5-디메틸헥실아민 등이 있다. 또한, 1급 아민형에 한하지 않고, 2급 아민형, 3급 아민형을 이용하는 것도 가능하다. 또한 이러한 유기물로서는 환상의 형상을 가질 수도 있다.
또한, 이용하는 분산제는 상기 알코올, 카르복실산, 아민을 포함하는 유기물에 한하지 않고, 알데히드기나 에스테르기, 술파닐기, 케톤기 등을 포함하는 유기물을 이용하는 것이 가능하다. 여기서, 피복이란 유기물 중의 관능기와 은 또는 산화은이 결합하고 있는 것이고, 응집을 막는 역할을 하는 것이다. 이러한 구조는 적외분광법을 이용하여 구별할 수 있다. 카르복실산이 은분이나 산화은의 주위를 피복할 때는 카르보닐염을 형성한다.
적외선 분광법을 이용하여 분산제 첨가의 은을 해석하면, 스펙트럼 해석을 행하면, 1520 cm-1 부근과 1420 cm-1 부근에 약한 피크가 나타난다. 이들 피크는 은과 결합하지 않는 경우에는 관측할 수 없다. 따라서 이와 같이 적외 분광 측정을 이용함으로써 입자를 피복하고 있는 유기물을 특정하는 것이 가능하다. 또한, 특정할 수 있는 유기물은 카르복실산뿐만이 아니라, 관능기를 갖는 유기물에 있어서는 어떤 물질을 이용하더라도 상기와 같이 특정이 가능하다.
<분산제의 혼합율>
분산제의 사용량은 은 입자와 산화은 입자의 합계를 100 질량부로 한 경우에 0.01 내지 20 질량부의 범위에서 이용할 수 있다. 이것은 분산제의 양이 0.01 질량부보다 적으면 은 입자와 산화은 입자의 분산성이 나빠서, 2차 응집을 일으켜, 접합 부분에의 균일한 도포가 곤란해져서, 무가압에서의 접합이 불가능해지기 때문이다. 또한, 20 질량부 이하로 한 것은, 20 질량부보다 많아지면, 접합 시의 은 입자끼리의 융합을 방해하게 되어, 접합 강도의 큰 저하가 보이기 때문이다.
은 입자와, 산화은 입자와, 탄소수 30 이하을 포함하는 분산제를 갖는 도전성 접합 재료에 있어서, 이들 혼합량은 전체 도전성 접합 재료 중에서 99.0 내지 100 중량％가 되도록 이용한다. 수지 결합제와 같은 것이 혼합되어 버리면, 은 입자 사이의 소결을 크게 저해하여, 접합 강도가 크게 저하되어 버리기 때문이다. 99.0 중량％로 한 것은, 불순물이 포함되어 있지 않은 은은 드물어, 통상 입수할 수 있는 은의 순도를 고려한 수치로 했기 때문이다.
<다른 조성물>
접합 재료 중에는 비교적 입경이 큰 평균 입경 0.1 ㎛ 내지 100 ㎛의 은 입자 이외의 입자를 혼합하여 이용하는 것도 가능하다. 이것은 도전성 접합 재료 중에 혼합된 은 입자와 산화은 입자가 평균 입경 0.1 ㎛ 내지 100 ㎛의 다른 금속 입자끼리를 소결시키는 역할을 하기 때문이다. 이 금속 입자의 종류로서는, 금, 구리을 들 수 있다. 상기 이외에도 백금, 팔라듐, 로듐, 오스뮴, 루테늄, 이리듐, 철, 주석, 아연, 코발트, 니켈, 크롬, 티탄, 탄탈, 텅스텐, 인듐, 규소, 알루미늄 등 중에서 1종 이상의 금속 또는 2종 이상의 금속으로 이루어지는 합금을 이용하는 것이 가능하다.
또한, 접합 재료 중에는 평균 입경이 100 nm 이하인 금속 입자를 미리 혼합하여 둘 수도 있다. 이러한 금속의 종류로서는 금, 은, 구리, 또는 이들 산화물인 산화금, 산화은, 산화구리를 들 수 있다. 상기 이외에도 백금, 팔라듐, 로듐, 오스뮴, 루테늄, 이리듐, 철, 주석, 아연, 코발트, 니켈, 크롬, 티탄, 탄탈, 텅스텐, 인듐, 규소, 알루미늄 등 중에서 1종 이상의 금속 또는 2종 이상의 금속으로 이루어지는 합금을 이용하는 것이 가능하다. 이들은 본 발명에 있어서의 도전성 접합 재료의 특성을 크게 저하시키지 않는 범위에서 혼합시켜 이용할 수도 있다.
다만, 이와 같이 다른 금속을 혼합한 경우에도 상술한 이유로부터 수지를 함유시키지 않아야 한다.
<페이스트상의 접합 재료>
본 실시 형태에서 이용되는 도전성 접합 재료는 은 입자와 산화은 입자와 분산제(다른 금속 입자도 포함)만으로 생성할 수도 있는데, 페이스트상의 접합 재료로서 이용하는 경우에는 비점이 350℃ 이하의 용매를 첨가하여 이용할 수도 있다. 이러한 용매로서는 예를 들면 알코올류 등을 들 수 있다. 여기서, 비점 350℃ 이하로 한 것은 접합 온도의 타겟이 200 내지 250℃이기 때문에, 너무 비점이 높으면 증발하는 데 너무 시간이 걸리기 때문이고, 350℃를 한도로 하는 것이 적당하다고 생각되기 때문이다. 다만, 그 온도를 초과하는 비점을 갖는 알코올류 등의 유기물이 절대로 부적당하냐고 한다면 그렇지 않다. 용도에 따라서는 그와 같은 유기물을 사용할 수도 있는 것은 물론이다.
이용 가능한 알코올기를 갖는 유기물로서는, 메탄올, 에탄올, 프로판올, 부틸알코올, 펜틸알코올, 헥실알코올, 헵틸알코올, 옥틸알코올, 노닐알코올, 데실알코올, 운데실알코올, 도데실알코올, 트리데실알코올, 테트라데실알코올, 펜타데실알코올, 헥사데실알코올, 헵타데실알코올, 옥타데실알코올, 노나데실알코올, 이코실알코올이 있다. 또한, 디에틸렌글리콜, 에틸렌글리콜, 트리에틸렌글리콜 등의 글리콜계를 사용할 수 있다. 나아가서는 1급 알코올형에 한하지 않고, 2급 알코올형, 3급 알코올형, 및 알칸디올, 환상형의 구조를 갖는 알코올 화합물을 이용하는 것이 가능하다. 그것 이외에도, 테르피네올, 에틸렌글리콜, 트리에틸렌글리콜, 또는 시트르산, 아스코르브산, 글루코오스 등 다수의 알코올기를 갖는 화합물을 이용할 수도 있다. 이 중에서도 특히 2급 알코올, 3급 알코올형의 화합물을 이용하는 것이 바람직하다. 이것은, 1급 알코올형으로서는 산화은과 혼합했을 때에 1일 후에는 산화은 표면의 일부를 환원하여 염을 형성함과 동시에 은 입자를 석출시켜 버려 산화은 입자의 보존 안정성이 나빠지기 때문이다. 2급 알코올, 3급 알코올형으로서는, 산화은과 반응하여 이러한 염이 표면에 형성되지 않기 때문에 안정성이 우수하다. 또한, 이들 중에서도 글리콜계의 용매를 이용하는 것이 바람직하다. 이것은 글리콜계의 용매는 저렴하고, 인체 등에 대한 독성도 적기 때문이다. 또한, 이들 알코올계의 용매는 용매로서 뿐만아니라, 산화은에 대한 환원제로서도 작용하는 것이 가능하기 때문에, 산화은 입자의 양에 대한 환원제로서 적절한 양으로 조정하여 사용할 수 있다.
또한, 상기 알코올기를 포함하는 유기물에 한하지 않고, 카르복실산, 아민, 알데히드기나 에스테르기, 술파닐기, 케톤기 등을 포함하는 유기물을 사용할 수 있다. 나아가서는, 상기한 바와 같은 관능기를 갖지 않는, 톨루엔이나, 탄화수소만으로 이루어지는 유기물을 이용할 수도 있고, 그와 같은 예로서는 헥산, 시클로헥산 등을 들 수 있다. 이와 같이 이용하는 유기 용제로서는 비점이 350℃ 이하이면 되고, 그와 같은 중에서는 1종만이 아니고, 2종 이상의 혼합물을 이용하는 것이 가능하다. 여기서, 350℃ 이하의 비점을 갖는 유기물이란 일반적으로 시판되고 있는 세이코 인스트루먼츠(Seiko Instruments) 제조의 TG/DTA6200나, 시마즈 세이사꾸쇼 제조의 TGA-50 등의 열중량 측정이 가능한 장치를 이용하여 10℃/분에 있어서 질소 중에서 측정을 행한 경우에 350℃까지 99 중량％의 중량 감소를 일으키는 유기물로 한다.
혼합하는 유기 용제의 양은 본 발명에 있어서의 도전성 접합 재료를 100 중량％로 한 경우에 90 중량％ 이내(보다 바람직하게는 50 중량％ 이내)이면 좋다. 이 때는 유발, 뇌궤기(grinding mixer), 진동 볼밀, 롤러 밀, 유성 볼밀 등을 이용하여 교반하여 혼합하면 좋다.
페이스트상의 도전성 접합 재료는 잉크젯법에 의해 미세한 노즐로부터 도전성 접합 재료를 분출시켜 기판 상의 전극 또는 전자 부품의 접속부에 도포하는 방법이나, 또는 도포 부분을 개구한 메탈 마스크나 메쉬 형상 마스크를 이용하여 필요 부분에만 도포를 행하는 방법, 디스펜서를 이용하여 필요 부분에 도포하는 방법, 실리콘이나 불소 등을 포함하는 발수성의 수지를 필요한 부분만 개구한 메탈 마스크나 메쉬 형상 마스크로 도포하거나 하는 방법이 있다. 이들 도포 방법은 접합하는 전극의 면적, 형상에 따라서 조합 가능하다. 또한, 이들 도전성 접합 재료에 가압을 가함으로써 시트상으로 성형하여 접합 재료로서 이용하는 방법이 있다.
<가열 조건>
본 도전성 접합 재료를 이용한 접합에서는, 접합 시에 은 입자끼리의 소결과 산화은의 환원 및 전극면과의 금속 접합을 달성하기 위해서 열을 가하는 것이 필수이다. 접합 조건으로서는, 1초 이상 180분 이내에서 40℃ 이상 350℃ 이하의 가열을 가하는 것이 바람직하다.
종래의 평균 입경이 100 nm 이하인 금속 입자에서는 유기물의 이탈에 수반하여 금속 입자가 부피 수축을 일으키기 때문에 접합 시의 가압이 필요하였지만 본 발명에서는 무가압으로 접합 계면에서의 금속 결합에 의한 접합이 달성 가능하다. 이에 따라 접합 공정의 간략화가 가능해진다. 그러나, 접합 강도 향상을 위해 필요가 있으면 가압하여 이용할 수도 있다.
가열 온도를 40℃ 이상으로 한 것은, 이것보다도 저온에서의 가열이면 은 입자의 소결과 산화은의 환원을 충분히 일으켜서 접합을 달성하는 것이 불가능하기 때문이다.
가열 시간을 180분 이하로 한 것은 가열 시간을 180분 이상으로 하면 하나의 제품을 제작하는 데 너무나 많은 시간이 걸려, 대량 생산을 행하는 것이 어려워지기 때문이다.
또한, 이 때의 접합 분위기로서는, 대기 중에 한하지 않고, 환원 분위기, 예를 들면, 수소 분위기, 또는 불활성 분위기인 질소 분위기, 아르곤 분위기 등을 이용하는 것이 가능하다. 이러한 분위기로 접합을 행함으로써 전자 부품 등의 대기 중 산화 등의 문제를 경감하는 것이 가능해진다.
본 발명의 (A) 은 입자, (B) 산화은, (C) 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제를 필수 성분으로 하는 전체 도전성 접합 재료 중에서, (A) 은분과 (B) 산화은분과 (C) 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제의 합계가 99.0 내지 100 중량％인, 도전성 접합 재료를 이용하여 접합된 반도체 장치의 접합부는 접합 시에 가압을 걸지 않기 때문에, 이용한 입자의 형상이 그대로 접합부에 반영된다.
따라서, 그 접합층에는 반드시 공극이 존재하여, 어떤 접합층의 단면을 본 때에 그 공극률(공공(空孔)을 접합층의 면적으로 나눈 것)은 0.1 내지 99.9％(보다 바람직하게는 90％ 이하)이다. 이와 같이 공극률이 존재함으로써 벌크 은으로 이루어지는 접합층보다도 밀도와 탄성률이 낮아져서, 칩에 대한 응력 부하가 경감되어, 접합부의 장기간 신뢰성이 높아진다.
[실시예]
이하, 본 발명의 실시예 및 적용예에 대해서 도면을 이용하여 설명한다.
<실시예 1>
실시예 1에서는 평균 입경이 1 ㎛ 정도, 평균 두께가 0.5 ㎛ 정도, 종횡비가 2.0 정도의 은 플레이크에 1.0 중량％의 스테아르산이 피복된 은 플레이크 0.9 g과 평균 입경이 약 2 ㎛ 정도의 산화은(Ag2O) 입자 0.1 g을 이용하고, 유기 용제에는 에탄올(와코 쥰야꾸 제조) 0.2 g을 이용하였다. 이들은 유발을 이용하여 1시간 정도 혼합을 행하여 도전성 접합 재료를 제작하였다.
비교예 1로서 시판되고 있는 종래 Ag 페이스트를 이용하였다. 또한, 비교예 2로서 평균 입경이 1 ㎛ 정도, 평균 두께가 0.3 ㎛ 정도, 종횡비가 2.0 정도의 은 플레이크에 1.0 중량％의 스테아르산이 피복된 은 플레이크 100 질량부에 대하여 20 질량부의 에탄올을 가하고 유발로 10분 정도 혼합한 도전성 접합 재료를 제작하였다.
다음으로 실시예 1과 비교예 1 내지 2의 도전성 접합 재료를 이용하여 접합을 행한 후, 전단 강도 측정을 행하였다. 측정용으로 이용한 시험편의 크기는 상측이 직경 5 mm, 두께 2 mm이고 하측이 직경 10 mm, 두께 5 mm인 것으로서, 표면에 Ag 도금이 된 것이다. 이 하측의 시험편의 위에 상기 실시예 1과 비교예 1 내지 2의 도전성 접합 재료를 도포한 후, 상측의 시험편을 접합 재료의 위에 설치하고, 200℃에서 가열함으로써 접합을 행하였다. 가열 시간은 5, 15, 30, 60분으로 행하였다(표 1 참조).
Figure 112010027131593-pat00001
도 1에 도시된 바와 같이, 접합 부재 (201)의 사이에 배치된 상기 도전성 접합 재료끼리가 가열에 의해 소결을 일으킴으로써 소결 은층 (205)이 형성된다. 이 때, 소결 은층 (205)과 접합 부재 (201)의 접합 계면은 금속 결합에 의한 접합이 달성된다. 다음으로, 상기 접합 재료를 이용하여 접합을 행함으로써 얻어진 시료를 이용하여 순수 전단 응력 하에서의 접합부 강도를 측정하였다. 전단 시험에는 세이신 쇼지 제조의 본드테스터 SS-100KP(최대 하중 100 kg)을 이용하였다. 전단 속도는 30 mm/분으로 하고, 시험편을 전단툴로 파단시켜 파단시의 최대 하중을 측정하였다. 이 최대 하중을 접합 면적으로 나누어서 전단 강도로 하였다.
도 2에 실시예 1과 비교예 1, 2의 접합 재료를 이용하여 얻어진 전단 강도 시험 결과를 나타낸다. 여기서 접합 강도의 값은 비교예 2의 시료를 이용하여 무가압으로 60분간, 200℃에서 가열한 경우의 접합 강도에 대한 상대비로 값을 나타내었다. 비교예 2의 평균 입경이 1 ㎛ 정도, 평균 두께가 0.3 ㎛ 정도, 종횡비가 2.0 정도인 은 플레이크에 1.0 중량％의 스테아르산이 피복된 은 플레이크 100 질량부에 대하여 20 질량부의 에탄올을 가하고 유발로 10분 정도 혼합한 도전성 접합 재료를 이용한 접합 재료로서는 접합 강도비가 낮지만, 실시예 1의 평균 입경이 1 ㎛ 정도, 평균 두께가 0.5 ㎛ 정도, 종횡비가 2.0 정도인 은 플레이크에 1.0 중량％의 스테아르산이 피복된 은 플레이크 0.9 g과 평균 입경이 약 2 ㎛ 정도인 산화은(Ag2O) 입자 0.1 g을 이용하고, 유기 용제에는 에탄올(와코 쥰야꾸 제조) 0.2 g을 이용하여, 유발에 의해 1시간 정도 혼합한 도전성 접합 재료에서는 접합 강도비가 크게 향상하여, 60분간 가열한 경우에는 상대 강도비로 2.0까지 되었다. 이것으로부터 은 플레이크에 산화은을 혼합함으로써 접합 강도가 크게 향상되는 효과를 확인할 수 있었다.
다음으로, 비교예 3 및 4와 실시예 1과의 비교를 행하였다. 비교예 3은 특허문헌 4(일본 특허 출원 제2006-353649)에 기재된 옥틸아민으로 피복된 은 나노 입자를 이용하였다. 비교예 4는 특허문헌 5(일본 특허 공개 제2008-178911)에 기재된 산화은 입자와 미리스틸알코올로 혼합된 접합 재료를 제작하였다. 비교예 5의 접합 재료는 산화은 입자(Ag2O)와 미리스틸알코올을 중량비에 있어서 9:1의 비율로 혼합하고, 유발에 의해 갈아서 제작하였다. 이들 재료를 이용하여 접합 강도 시험을 행하였다. 측정용으로 이용한 시험편의 크기는 상측이 직경 5 mm, 두께 2 mm이고 하측이 직경 10 mm, 두께 5 mm의 것으로, 표면에 Ag 도금이 된 것이다. 이 하측의 시험편의 위에 상기 비교예 3 및 4의 도전성 접합 재료를 도포한 후, 상측의 시험편을 접합 재료의 위에 설치하고, 200℃에서 가열함으로써 접합을 행하였다. 접합 강도는 순수 전단 응력 하에서의 접합부 강도를 측정하였다. 전단 시험에는 세이신 쇼지 제조의 본드테스터 SS-100KP(최대 하중 100 kg)을 이용하였다. 전단 속도는 30 mm/분으로 하여, 시험편을 전단툴로 파단시키고, 파단시의 최대 하중을 측정하였다. 이 최대 하중을 접합 면적으로 나누어서 전단 강도로 하였다. 표에 나타낸 바와 같이 접합 강도비로 비교를 행하였다. 이와 같이 종래의 금속 접합을 달성할 수 있는 접합 기술과 비교하면 큰 접합 강도의 향상이 보여, 본 발명의 도전성 접합 재료가 우수한 특성을 갖고 있는 것을 알 수 있다(상기 표 1 참조).
<실시예 2>
실시예 2에서는 평균 입경이 1 ㎛ 정도, 평균 두께가 0.5 ㎛ 정도, 종횡비가 2.0 정도인 은 플레이크를 이용하였다. 그리고, 1.0 중량％의 스테아르산이 피복된 은 플레이크에 대하여 평균 입경이 약 2 ㎛ 정도의 산화은(Ag2O) 입자를 혼합시키는 비율을 중량비에 있어서 95:5, 90:10, 80:20, 50:50으로 변화시켜 시료를 제작하였다. 또한, 각각의 시료 100 질량부에 대하여 유기 용매로서 에탄올(와코 쥰야꾸 제조) 20 질량부를 혼합하고, 유발을 이용하여 1시간 정도 혼합을 행하여 각각 1 g의 도전성 접합 재료를 얻었다. 그 후 전단 강도의 측정을 행하였다. 측정용으로 이용한 시험편의 크기는 상측이 직경 5 mm, 두께 2 mm이고 하측이 직경 10 mm, 두께 5 mm의 것으로, 표면에 Ag 도금이 된 것이다. 이 하측의 시험편의 위에 상기 실시예 1과 비교예 1 및 2의 도전성 접합 재료를 도포한 후, 상측의 시험편을 접합 재료의 위에 설치하고, 200℃에서 가열함으로써 접합을 행하였다. 가열 시간은 60분이다. 각각의 강도는 비교예 2의 시료를 이용하여 무가압으로 60분간, 200℃에서 가열한 경우의 접합 강도에 대한 상대비로 값을 나타내었다.
도 3에 도시된 결과와 같이 산화은(Ag2O) 입자를 5 중량％ 혼합시킨 경우에 가장 높은 접합 강도가 얻어진다. 이것은 가한 스테아르산과 산화은 입자의 산화환원하는 비율이 최적의 비율이었기 때문이다. 산화은이 많으면, 산화은이 남고, 또한 산화은이 적으면, 은 플레이크의 주위의 유기물이 없어지지 않기 때문에, 접합 강도의 대폭적인 향상이 보이지 않게 된다.
다음으로, 실시예 2, 비교예 1 내지 4의 열전도율 측정의 값을 비교하였다. 열전도율은 수학식 1로 정의된다.
Figure 112010027131593-pat00002
열전도율을 산출하기 위해서 필요한 열확산율(m2/s), 밀도(g/cm3), 비열(J/g?K)은 이하의 장치를 이용하여 측정하였다. 열확산율은 샘플 형상을 5 mm×10 mm×0.1 ㎛로 하고, 울박 신쿠-리코(ULVAC SINKU-RIKO) 제조의 PIT1형에 의해 측정하였다. 밀도는 알파 미라쥬 제조의 SD-200L에 의해 측정하였다. 또한, 비열은 TA 인스트루먼트(TA instrument) 제조의 Q2000에 의해 측정하였다. 이들 값을 이용하여 열전도율을 산출하였다. 표 2에 결과를 나타내었다.
이 값은, 비교예 2의 시료를 이용하여 무가압으로 60분간, 200℃에서 가열한 경우의 열전도율에 대한 상대비로 나타내었다. 비교예 1과 3과 4에서는 열전도율의 값이 비교예 2보다도 작다. 이것은 접합 강도와도 대응하고 있고, 비교예 1에서는 열전도율이 작은 수지를 혼합하고 있기 때문에, 비교예 3과 4에서는 가압을 걸지 않기 때문에 밀도가 작기 때문이다. 그러나, 실시예 2(여기서는 은 플레이크와 산화은 입자를 혼합시키는 비율을 중량비에 있어서 90:10의 시료를 이용함)에서는 비교예 2보다도 큰 열전도율을 갖고 있었다. 이것은 산화은을 혼합함으로써 소결 온도가 낮아져서, 동일 온도에 있어서도 제작된 필름의 소결이 보다 진행하고 있었기 때문이다. 이상으로부터, 실시예 2의 접합 재료는 접합 강도뿐만아니라, 열전도율에 있어서도 우수하다.
Figure 112010027131593-pat00003
<적용예 1>
도 4는 본 발명의 적용예의 하나인 비절연형 반도체 장치의 구조를 도시한 도면이다. 도 4의 (a)는 상면도, 도 4의 (b)는 도 4의 (a) A-A'부의 단면도이다. 반도체 소자(MOSFET) (301)를 세라믹 절연 기판 (302) 상에 세라믹 절연 기판 (302)을 베이스재 (303) 상에 각각 탑재한 후, 에폭시계 수지 케이스 (304), 본딩 와이어 (305), 에폭시계 수지제의 덮개 (306)을 설치하고, 동일 케이스 내에 실리콘겔 수지 (307)를 충전하였다. 여기서, 베이스재 (303) 상의 세라믹 절연 기판 (302)은 실시예 1의 도전성 접합용 재료를 이용하여 접합된 접합층 (308)로 접합되고, 세라믹 절연 기판 (302)의 구리판 (302a) 상에는 8개의 Si로 이루어지는 MOSFET 소자 (301)가 상기 실시예 1의 도전성 접합 재료에 의해 접합된 접합층 (309)로 접합되어 있다. 이 접합층 (308) 및 (309)에 의한 접합은, 우선, 세라믹 절연 기판 (302)의 구리판 (302a)(Ni 도금이 실시되어 있음) 상, 및 베이스재 (303) 상에 실시예 1의 도전성 접합 재료를 각각 도포한다.
그리고, 실시예 1에서 나타낸 도전성 접합 재료의 위에 반도체 소자 (301), 및 세라믹 절연 기판 (302)을 배치시켜 접속한다. 이 때 대기 중에서 150℃ 정도에서 120분간 가열함으로써 접합을 행하였다.
각 소자 (301)에 형성된 게이트 전극, 이미터 전극 등과, 절연 기판 상에 형성한 전극 (302a), (302b), 에폭시계 수지 케이스 (304)에 미리 부착되어 있는 단자 (310)의 사이는, 직경 300 ㎛의 Al선 (305)을 이용하여 초음파 접합법에 의해 와이어 본딩하였다. (311)은 온도 검출용 써미스터 소자로서, 실시예 1의 도전성 접합 재료에 의해 접합된 접합층 (309)으로 구성되고, 전극 (302b)와 단자 (310) 사이를 직경 300 ㎛의 Al선 (305)으로 와이어 본딩하여 외부로 연락되어 있다.
또한, 에폭시계 수지제의 케이스 (304)와 베이스재 (303)의 사이는 실리콘 접착 수지(도시하지 않음)을 이용하여 고정하였다. 에폭시계 수지제의 덮개 (306)의 내후부(內厚部)에는 오목부 (306'), 단자 (310)에는 구멍 (310')이 각각 설치되고, 절연형 반도체 장치 (1000)을 외부 회로와 접속하기 위한 나사(도시하지 않음)이 장착되도록 되어 있다. 단자 (310)는 미리 소정 형상으로 펀칭, 성형된 구리판에 Ni 도금을 실시한 것으로서, 에폭시계 수지 케이스 (304)에 부착되어 있다.
도 5는 도 4에 도시된 절연형 반도체 장치의 서브어셈블리부를 도시한 도면이다. 해당 절연형 반도체 장치는 세라믹 기판과 반도체 소자를 베이스재로서의 복합재 (303)에 탑재하고 있다. 베이스재에는 주변부에 설치 구멍 (303A)가 형성되어 있다. 베이스재는 Cu로 구성되어 있고, 표면에 Ni 도금이 실시되어 있다. 베이스재 (303) 상에는 실시예 1의 도전성 접합 재료에 의한 접합층으로 세라믹 절연 기판 (302)를, 그리고 세라믹 절연 기판 (302) 상에도 마찬가지로 실시예 1의 도전성 접합 재료에 의해 접합된 접합층에 의해 MOSFET 소자 (301)가 각각 탑재되어 있다. 이 때의 접합은 대기 분위기에서 항온조를 250℃에서 60분간 가열함으로써 접합되어 있다.
도 6은 도 5에 있어서의 MOSFET 소자 탑재부의 접합전의 단면의 확대 개략도이다. 도 6에 나타낸 바와 같이, 접합층에 실시예 1의 도전성 접합용 재료를 이용하는 것이 가능하다. 또한 실시예 1의 도전성 접합 재료의 도포 시의 용액 흐름 방지를 위해 베이스재 (303) 상에는 세라믹 절연 기판 (302) 탑재 영역에 대응하도록 발수막 (322)이 실시되어 있다. 또한, 세라믹 절연 기판 (302) 상에는, 반도체 소자 (301)의 탑재 영역에 대응하도록 발수막 (321)이 실시되어 있어, 상기 페이스트 도포 시의 용액 흐름 방지를 도모하고 있다.
<적용예 2>
적용예 2는, 셀룰러 전화기 등의 송신부에 이용하는 고주파 전력 증폭 장치로서의 절연형 반도체 장치에 관한 것이다. 해당 절연형 반도체 장치(크기 10.5 mm×4 mm×1.3 mm)의 구성은 이하에 나타내는 것과 같다.
도 7은 적용예 2에 의한 절연형 반도체 장치의 단면 모식도이다. 여기서는, 지지 부재 (100)으로서의 다층 유리 세라믹 기판(크기 10.5 mm×4 mm×0.5 mm, 3층 배선, 열팽창율 6.2 ppm/℃, 열전도율 2.5 W/mK, 굽힘 강도 0.25 GPa, 영률 110 Gpa, 유전율 5.6(1 MHz)) 상에, MOSFET 소자(크기 2.4 mm×1.8 mm×0.24 mm) (1), 칩 저항(약 7 ppm/℃) (101), 칩컨덴서(약 11.5 ppm/℃) (102)를 포함하는 칩 부품이 탑재되어 있다.
MOSFET 소자 (1)과 다층 유리 세라믹 기판 (100)의 사이에는, 예를 들면 Cu-Cu2O 복합재로 이루어지는 중간 금속 부재 (103)가 장비되어 있다. 다층 유리 세라믹 기판 (100)의 내부에는 후막(厚膜) 내층 배선층(Ag-1 중량％ Pt, 두께 15 ㎛), 다층 배선 사이의 전기적 연락을 위한 후막 관통 구멍 도체(Ag-1 중량％ Pt, 직경 140 ㎛), 방열로를 위한 후막 서멀비어(Ag-1 중량％ Pt, 직경 140 ㎛)이 설치되어 있다.
또한, 다층 유리 세라믹 기판 (100)의 한쪽의 주요면 상에 후막 배선 패턴(Ag-1 중량％ Pt, 두께 15 ㎛) (104)가 설치된다. 이 후막 배선 패턴 (104) 상에는 칩 저항 (101), 칩 컨덴서 (102)를 포함하는 칩 부품이 탑재되는데, 우선 실시예 1의 도전성 접합 재료에 있어서 유기 용매에 에탄올 대신에 데칸올을 동일한 정도 가하고 유발로 10분간 혼합하여 페이스트상으로 한 후, 후막 배선 패턴 상에 도포하고, 수소 치환한 항온조 중에서 200℃에서 30분간 가열함으로써 소결 은층 (105)에 의해 도전적으로 칩 부품이 고착되어 있다.
MOSFET 소자(Si, 3.5 ppm/℃) (1)은 다층 유리 세라믹 기판 (100)의 한쪽의 주요면에 설치한 오목부의 부분에 중간 금속 부재 (103)를 통해 탑재된다. 탑재는 10의 마이너스 3승의 진공 중에서 행하였다. 중간 금속 부재 (103)의 크기는 2.8 mm×2.2 mm×0.2 mm이다. 여기서, MOSFET 소자 (1)과 중간 금속 부재 (103)를 접속하는 소결 은층 (105)나, 중간 금속 부재 (103)과 다층 유리 세라믹 기판 (100)을 접속하는 접합층 (106)은 모두 실시예 1의 도전성 접합 재료에 있어서 유기 용매에 에탄올 대신에 데칸올을 동일 정도 가하고 유발로 10분간 혼합하여 페이스트상으로 한 도전성 접합용 페이스트 재료를 이용하여 접합된 층이다. MOSFET 소자 (1)과 후막 배선 패턴 (104)의 소정부 사이에는 Cu로 이루어지는 클립형의 접속 단자 (107)은 실시예 1의 도전성 접합용 재료를 이용하여 접합되어 있다. 이 때의 접합은 수소 치환한 항온조 중에서 200℃에서 30분간 가열하여 행하였다. 다층 유리 세라믹 기판 (100)의 다른쪽의 주요면에는, 후막 외부 전극층 (104')(Ag-1 중량％ Pt, 두께 15 ㎛)가 설치되어 있다. 후막 외부 전극층 (104')은 다층 유리 세라믹 기판 (100)의 내부에 설치된 내부 배선층이나 관통 구멍 배선을 중계하고 후막 배선 패턴 (104)과 전기적으로 접속되어 있다. 다층 유리 세라믹 기판 (100)의 한쪽의 주요면측에는 에폭시 수지층 (108)이 설치되고, 이에 따라 탑재칩 부품 등은 밀봉되어 있다.
<적용예 3>
적용예 3은 미니 몰드형 트랜지스터용의 리드 프레임으로서 복합재를 적용한 비절연형 반도체 장치에 관한 것이다.
도 8은 적용예 3에 의한 미니 몰드형 비절연형 반도체 장치의 단면 모식도이다. 반도체 소자 (1)로서의 Si로 이루어지는 트랜지스터 소자(크기 1 mm×1 mm×0.3 mm)는 예를 들면 Cu-Cu2O 복합재로 이루어지는 리드 프레임(두께 0.3 mm) (600)에 실시예 1의 도전성 접합용 재료를 도포한 후, 질소 치환된 항온조에서 200℃에서 60분간 가열을 행함으로써 소결 은층 (601)에 의해 접합되어 있다. 트랜지스터 소자 (1)의 콜렉터도 실시예 1의 도전성 접합 재료를 이용하여 접합된 측에 배치되어 있다. 이미터 및 베이스는 실시예 1의 도전성 접합 재료에 의해 접합된 측과 반대측에 설치되고, 트랜지스터 소자 (1)로부터 인출된 클립 형상의 단자 (602)에 의해 리드 프레임 (600)에 실시예 1의 도전성 접합 재료를 도포하여, 클립 형상의 단자에 마찬가지로 질소 치환된 항온조에서 200℃에서 60분간의 가열을 가함으로써 접합되어 있다. 또한, 트랜지스터 소자 (1)의 탑재와 클립 형상의 단자 (602)가 실시된 주요부는 트랜스퍼 몰드에 의해서 에폭시 수지 (603)로 덮여져 있다. 리드 프레임 (600)은 에폭시 수지 (603)에 의한 몰드가 완료한 단계에서 분리되고, 각각 독립한 단자로서의 기능이 부여된다.
<그 밖의 적용예>
LED를 기판에 실장할 때에 본 발명의 도전성 접합 재료를 이용하여 접합을 행함으로써 종래의 땜납, Ag 페이스트 도전성 접착재보다도 방열성을 향상시키는 것이 가능해진다.
201 : 접합 부재
202 : Ag 플레이크
203 : Ag2O
205 : 소결 은층
301 : 반도체 소자
302 : 세라믹 절연 기판
302a : 구리판
303 베이스재
304 : 에폭시계 수지 케이스
305 : 본딩 와이어
306 : 에폭시계 수지 덮개
307 : 실리콘겔 수지
308, 309 : 접합층
310 : 단자

Claims (11)

  1. 은 입자와, 산화은 입자와, 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제를 필수 성분으로 하고, 상기 은 입자와 상기 산화은 입자와 상기 분산제의 합계가 99.0 내지 100 중량％인 것을 특징으로 하는 도전성 접합 재료.
  2. 제1항에 있어서, 상기 은 입자와 상기 산화은 입자의 입경이 0.1 ㎛ 이상 100 ㎛ 이하인 것을 특징으로 하는 도전성 접합 재료.
  3. 제1항에 있어서, 상기 은 입자가 플레이크 형상을 하고 있는 것을 특징으로 하는 도전성 접합 재료.
  4. 제1항에 있어서, 상기 은 입자 및 상기 산화은 입자의 적어도 한쪽이 상기 분산제에 의해 피복되어 있는 것을 특징으로 하는 도전성 접합 재료.
  5. 제1항에 있어서, 상기 은 입자와 상기 산화은 입자의 혼합율은, 상기 은 입자를 100 질량부로 한 경우에, 상기 산화은 입자가 0.01 질량부 이상 100 질량부 이하인 것을 특징으로 하는 도전성 접합 재료.
  6. 제5항에 있어서, 상기 산화은 입자의 양은 상기 분산제의 양 이하인 것을 특징으로 하는 도전성 접합 재료.
  7. 은 입자와, 산화은 입자와, 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제와, 비점이 350℃ 이하인 유기 용제를 필수 성분으로 하며,
    상기 은 입자와 상기 산화은 입자와 상기 분산제와 상기 유기 용제의 합계를 100 질량부로 한 경우에, 상기 유기 용제의 양이 0 질량부 초과 90 질량부 이하이고,
    상기 은 입자와 상기 산화은 입자와 상기 분산제와 상기 유기 용제와의 합계가 99.0 내지 100 중량％이고, 페이스트상을 하고 있는 것을 특징으로 하는 도전성 접합 재료.
  8. 은 입자와, 산화은 입자와, 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제와, 은 이외의 금속 입자를 필수 성분으로 하고,
    상기 은 입자와 상기 산화은 입자와 상기 분산제와 상기 은 이외의 금속 입자와의 합계가 99.0 내지 100 중량％이고,
    상기 은 이외의 금속 입자는 금, 산화금, 구리, 산화구리 중에서 선택된 1종이상의 금속, 또는 백금, 팔라듐, 로듐, 오스뮴, 루테늄, 이리듐, 철, 주석, 아연, 코발트, 니켈, 크롬, 티탄, 탄탈, 텅스텐, 인듐, 규소, 알루미늄 중에서 선택된 1종 이상의 금속 또는 2종 이상의 금속으로 이루어지는 합금인 것을 특징으로 하는 도전성 접합 재료.
  9. 은 입자와, 산화은 입자와, 탄소수 30 이하로 구성되는 유기물을 포함하는 분산제와, 비점이 350℃ 이하인 유기 용제와, 은 이외의 금속 입자를 필수 성분으로 하며,
    상기 은 입자와 상기 산화은 입자와 상기 분산제와 상기 유기 용제와 상기 은 이외의 금속 입자의 합계를 100 질량부로 한 경우에, 상기 유기 용제의 양이 0 질량부 초과 90 질량부 이하이고,
    상기 은 입자와 상기 산화은 입자와 상기 분산제와 상기 유기 용제와 상기 은 이외의 금속 입자와의 합계가 99.0 내지 100 중량％이고, 페이스트상을 하고 있고,
    상기 은 이외의 금속 입자는 금, 산화금, 구리, 산화구리 중에서 선택된 1종이상의 금속, 또는 백금, 팔라듐, 로듐, 오스뮴, 루테늄, 이리듐, 철, 주석, 아연, 코발트, 니켈, 크롬, 티탄, 탄탈, 텅스텐, 인듐, 규소, 알루미늄 중에서 선택된 1종 이상의 금속 또는 2종 이상의 금속으로 이루어지는 합금인 것을 특징으로 하는 도전성 접합 재료.
  10. 제1항에 기재된 도전성 접합 재료를 이용하여 접합되고, 접합부가 금속 부분만으로 이루어지고, 그의 공극률이 0.1％보다 크고 90％보다 작은 것을 특징으로 하는 반도체 장치.
  11. 반도체 소자의 전극과 금속 부재와의 사이에 제1항에 기재된 도전성 접합 재료를 배치하고, 수소 중, 질소 중 또는 아르곤 분위기 중에서 가열함으로써 상기 도전성 접합 재료를 소결시켜, 상기 반도체 소자의 전극과 상기 금속 부재를 금속 접합하는 것을 특징으로 하는 접합 방법.
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